Manufacture of new polymerization products



y 1938. a R. |-m 2,117,3 21

MANUFACTURE OF NEW POLYMERIZATION PRODUCTS Filed Dec. 1, 1932 INVENTOR'.

R clwland Hill ATTORNEY.

Patented May 17, 1938 2,117,321

UNITED ETATES PATENT orFlcE MANUFACTURE OF NEW POLYMER!- TION PRODUCTS Rowland mu, Blackley, Manchester, England.

assignor to Imperial Chemical Industries Limited, a corporation of Great Britain Application December 1, 1982, Serial No. 645,318 In Great Britain December 2, 1981 17 Claims. (Cl. 289-2) This invention relates to the manufacture of products are made by subjecting to polymerization polymerization products possessing charactera mixture of the hitherto unknown methyl istic and valuable physical properties. which methacrylate and a suitable proportion of at render them valuable for use as ingredients in least one polymerizable material and particu- 5 coating compositions, for use-as molding composila rly polymerizable unsaturated esters and even 5 tions either by themselves or admixed with other more specifically those containing an ethylenic ingredients, and for use in the manufacture of linkage conjugated with a multiply bonded carunsplinterable glass. bon, i. e. HzC=CC=c or Elm-'05s, or

It has been proposed to use the polymerization those containing a doubly bonded carbon directly products of methyl or ethyl acrylate or mixtures of attached to a negative group. such as esters oi m the two in the manufacture of compound glass, acrylic acid, e. g. methyl acrylate; or other esters and it has been proposed to use various other subof methacrylic acid, e. g. butyl methacrylate: stances, for instance,a polymerized itaconic ester. vinyl esters, e. g. vinyl acetate, vinyl chloride,

a polymerized ethyl ester of crotonlc acid, and styrene, vinyl cyanide; itaconic esters, e. g. di-

l5 polymerized vinyl esters not to mention such mlxmethyl itaconate. Interpolymers are also obtures as contain cellulose esters. tained in accordance with the invention by poly- Unsplinterable glass consists of a sandwich of merizing methyl methacrylate with polymerizable an interlayer of transparent material between two materials such as acrolein, methyl vinyl ketone, sheets of common glass, the interlayer material synthetic resins in the initial stages of polymerizaacting also as a cement, or being fixed to the tion, e. g. high acid number polyhydric alcoholm glass by a separate cementing medium. It is the polybasic acid condensation products, incominterlayer thus cemented which-prevents the glass pietely polymerized phenol formaldehyde resins, from spllntering when fractured, and a good interurea-formaldehyde resins, ptoluenesulionamldelayer material should be hard, tough, sufllcientiy formaldehyde resins, etc.

elastic to draw back splintered glass, and should The hitherto unknown methyl methacrylate give an even surface, transparent, and colorless, may be obtained by treating methyl s-hydroxyand it should conserve these properties so long as iso-butyrate with a dehydrating agent, e. g. phosthe material is in use and over the range of temphorus pentoxide, as more fully described in my peratures usually covered by climatic changes. copendlng application, Serial No.'641,113, filed Consequently to provide a suitable interlayer Nov. 3. 1932, on which U. 8. Patent 1,980,483 was 30 material is a problem the solution of which is granted Nov. 13, 1934. It may also be prepared only being reached bystages, and the proposals by the method described in the application 0! above referred to have not, in my experience, pro- Donald J. Loder, filed February 8, 1932, Serial No. vided a fully satisfactory solution. 598,411, 1. e. by chlorination of isobutyric acid,

The present invention is directed particularly to esteriflcation of the chlor-acid with methyl the solution of this problem. alcohol and dehalogenation of the chlor-ester.

The physical properties of the polymerization In the present specification the generally acproducts obtained according to the invention are, cepted term methacryla te" is used as a conhowever. such that the products find valuable venient synonym for a-methylacrylate (cf. von 40 application also in the manufacture of molded Richters- Organic Chemistry. translated by 40 bodies and coating compositions. Splelmann, London, 1919, Vol. I, p. 297). Other The hitherto unknown methyl methacrylate methacrylates are obtained by similar means from (methyl a-methyl-acryiate) is converted on polythe corresponding hydroxy-iso-butyric esters. merization, for example, by the methods described The polymerization is effected by subjecting the as applicable to organic vinyl esters in British mixture to the action of radiant energy (heat 45 specification No. 15,271/1914 into a very hard and/or light), oxygen, or oxygen-containing subtough glassy mass, which has a concholdal fracstances, separately or together. Any of the polyture and can be pulverized. Because of its hardmerization promoting means known (cf. British ness and lack of elasticity this material cannot be specification No. 15,2'11/1914) may be used, but an used by itself in the manufacture oi unsplinterable I preferably use benzoyl or other peroxides. The glass, altho it is so tough. Known methacrylates, polymerization may be eifected in a solvent, e. g. and the alkyl esters of acrylic acid itself, on the toluene. and the operation may be carried out other hand, all yield on polymerization either under pressure. The substance may also be brittle masses or soft rubber-like flexible products. emulsified and then polymerized. 66 According to the invention new polymerization l The polymerization products so obtained are both hard and very tough. They are soluble in ester, ketone, and aromatic. hydrocarbon solvents. In these as in other properties they differ'i'rom mere mixtures of the separately polymerized ingredients. The properties naturally vary according to the proportions of the ingredients but the relationships between properties and composition are not linear. Evidently polymerization takes place in such a way that the chains of monomer residues produced are mixed and the nature of the product depends on the particular way in which these mixed chains are formed.

When the interpolymers of the present invention are used as the interlayer in safety'glass combinations they may form both interiayer and adhesive therefor or a separate adhesive may be used. As adhesives, gelatin, casein, cellulose derivatives, such as the acetate, nitrate, ethyl ether, etc., resins such as polyhydric alcohol-polybasic acid resins, dephenyloipropane-al ehyde resins, toluenesulfonamide-aldehyde resins, vinyl resins, etc. may be used. When no separate adhesive is used the interlayer is preferably caused to adhere to the glass layers by means of heat and pressure with or without the aid of added solvent and/or plasticizer, In general an interpolymer containing from l0-:'75% methyl methacrylate is preferred as an inter-layer material. Mixtures of these interpolymers with natural or synthetic resins, cellulose derivatives, or other plastic materials may be used.

When the new polymerization products are to be used in the production of molded bodies, they are, if necessary, pulverized, and are then molded, with or without the addition of fillers, plasticizers, pigments, dyes, or other thermoplastic resinous materials, by a heat and pressure treatment. The molding may also be carried out by an extrusion process, the polymerization product being put into an appropriate container and heated to a temperature at which it is sufficiently plastic, and being then extruded by pressure into a cooled mold.

The polymerization products are also valuable for the manufacture of flexible transparent films,

such as cinematograph films.

The polymerization products are also valuable for use as ingredients in coating compositions, such as lacquers, enamels and the like. The properties of the coating compositions can be modified over a wide range by the addition of film-forming. materials such as cellulose esters and ethers, e. g. nitrocellulose, cellulose acetate,

and ethyl and benzyl cellulose, and/or plasticizers, e. g. dibutyl phthalate and tricresylphosphate. Pigments, extenders, dyestuffs, fatty oils of the drying, semi-drying or non-drying type,

and syntheticand natural resins may also be added.

The invention is illustrated but not limited by the following examples in which the parts are by weight.

Example 1.-l part of methyl methacrylate B. P. 100-101 C. and 3 parts of methyl acrylate B. P. 78-81 C. are mixed. 0.04 part of benzoyl peroxide is added. The mixture is heated to 55-60 C. for 16 hours.

The resulting mass is very pale straw in color. It is moderately hard, elastic and very tough. It dissolves in such organic solvents as toluene, ethyl and butyl acetates, and glycol monoethyl ether. It may be rolled when warm (e. g. at 45-50 C.) into tough elastic sheets.

Example 2.-10 parts of methyl methacrylate B. P. 100-101 C. and 10 parts of ethyl acrylate B. P. 98-101" C. are mixed. 0.2 part of benzoyl peroxide is added and the mixture is heated for 4 hours at 100 C.

The product is almost colorless and does not discolor on exposure to light. It is hard and tough. It may be milled on rolls like the product of Example 1 to give transparent tough sheets. It is soluble in organic solvents and compatible with nitrocellulose. I

Example 3.1 part of methyl methacrylate and 3 parts of n-butyl methacrylate are mixed. 0.04 part of benzoyl peroxide is added, and the mixture is heated for 8 hours at 100 C.

The product is moderately hard and tough, and resembles the products of the preceding examples. n-butyl methacrylate may be obtained from n-butyl a-hydroxy-iso-butyrate by dehydration e. g. with phosphorus pentoxide.

Example 4.1 part of vinyl acetate, 2 parts of methyl methacrylate and 0.015 part of benzoyl peroxide are mixed and heated at C. Polymerization begins after about two hours, and is substantially complete after 18 hours. -The new polymerization product obtained is a hard, tough, colorless product with a high softening point.

For molding the product is pulverized and, for example, 10 grams are introduced into a flash type disc mold 2 inches in diameter, which is then heated at 120 C. for 2 minutes under a pressure of -2 tons per sq. inch. The mold is cooled to C. and the molding ejected. A transparent tough disc is obtained.

Example 5.-3 parts of methyl methacrylate and one part of acrylic nitrile are mixed and 0.04 part of benzoyl peroxide is added. The mixture is heated at 60 C. for 18 hours.

The new polymerization product so obtained is pale yellow in color. This is hard, tough and resilient, and possesses high tensile strength and impact resistance. It may be molded asdescribed in Example 4.

Example 6.2 parts of methyl methacrylate are mixed with 1 part of methacrylic nitrile, 0.03 part of benzoyl peroxide is added and the mixture heated at 60 C. for 20 hours, then at C. for 9 hours.

The product is pale straw in color, transparent, hard and tough.

Example 7.-l part of methyl methacrylate and 1 part of methyl acrylate are mixed. 0.006

part of sodium perborate and 0.03 part of acetic anhydride are added and the mixture is then heated at 60 C. for 30 hours, when polymerization appears to be complete.

The so obtained polymerization product is hard, tough, flexible, transparent and colorless.

Example 8.l0 parts of methyl methacrylate and 15 parts of methyl acrylate are mixed with 0.12 part of benzoyl peroxide, and the mixture is heated for 4 hours at C. and then for 4 hours at C. under a pressure oi. 300 lbs. per sq. inch.

The resulting interpolymer is colorless, transparent, moderately elastic and very tough. It can be rolled into sheets which are then well suited for use in the manufacture of compound safety glass.

Example 9.A mixture of ten parts of methyl methacrylate and 15 parts of methylacrylate containing 0.25 part of benzoyl peroxide is added slowly with rapid stirring to .a solution of 1 part of sodium iso-propylnaphthalene-sulfonate and Ofggarg of Turkey-red oil in 100 parts of water 9. 4

The emulsion produced is heated for 12 hours at C. and cooled. 1 part of aqueous hydrogen peroxide (20 vols.) is then added, and the mixture is heated again, at C., for a further 4 hours.

After cooling, the emulsion is coagulated by pouring it with rapid stirring into 250 parts of 3.5% hydrochloric acid. The white coagulum is filtered off, washed free from acid, and dried.

The dried product is soluble in a wide range of common organic solvents and is compatible with nitrocellulose.

Example 10.10 parts of methyl methacrylate and 10 parts of methyl vinyl ketone are mixed with 25 parts of butyl acetate and 0.1 part of benzoyl peroxide and heated for 8 hours under a reflux condenser. The resulting product is a viscous, transparent, very pale yellow -mass, soluble in additional solvent and thus suitable in the preparation of lacquers and safety glass.

Example 11.10 parts of methyl methacrylate and 10 parts of vinyl acetate are mixed with 0.1 part of benzoyl peroxide and heated for 10 hours under super-atmospheric pressure at 80 C. The product is a water white, transparent, hard, tough, solid, soluble in ester ketone and aromatic hydrocarbon solvents.

Example 12.2 parts of methyl methacrylate and 8 parts of vinyl chloride are mixed with 20 parts of toluene and 0.05 part of benzoyl peroxide and heated for 12 hours, at C. in a closed container or passed under pressure thru a tube heated to 105 C. at such a rate that they remain in the heated zone for the same length of time. The product is transparent, slightly yellow, and soluble in aromatic hydrocarbon solvents.

Polymerization under the influence of heat ization products comprising subjecting to polymerizing conditions, a mixture containing methyl than one bond.

3. Process for the manufacture of new polymerization products comprising subjecting to polymerizing conditions a mixture containing methyl methacrylate and an ester of acrylic acid.

4. Process for the manufacture of new polymerization products comprising subjecting to polymerizing conditions a mixture containing methyl methacrylate and an ester of methacrylic acid.

6. Process for the manufacture of new polymer ization products comprising subjecting to polymerizing conditions a mixture containing methyl methacrylate and butyl methacrylate.

7. Process for the manufacture of new polymerization products comprising subjecting to polymerizing conditions a mixture containing methyl methacrylate and a vinyl ester.

8. Process for the manufacture of new polymerization products comprising subjecting to polymerizing conditions a mixture containing methyl methacrylate and vinyl acetate.

9. As a new article of manufacture a resin having the properties of the product obtained by polymerizing a mixture of methyl methacrylate and at least one other polymerizable organic material.

10. As a new article of manufacture a resin having the properties of the product obtained by polymerizing a mixture of methyl methacrylate and at least one other polymerizable organic material -containing the grouping H2C=cCX :where X is-joined to carbon by more than one bond.

11. A plastic mass comprising the product of joint polymerization of methyl methacrylate and an acrylic acid ester.

12. A plastic mass comprising the product of joint polymerization'of methyl methacrylate and methyl acrylate.

13. The product of joint polymerization of a mixture comprising methyl methacrylate and another derivative'of methacrylic acid.

-14. The product of joint polymerization of a mixture comprising methyl methacrylate and another ester of methacrylic acid.

15. The product of joint polymerization of a mixture comprising methyl methacrylate and another lower alkyl ester of methacrylic acid.

16. The product of joint polymerization of a mixture comprising methyl methacrylate and another unsaturated polymerizable organic compound irom the group consisting of vinyl esters and esters of acrylic and methacrylic acids.

1'1. Process for the manufactureof new polymerization products comprising subjecting to polymerizing conditions a mixture containing methyl methacrylate and another unsaturated polymerizable organic compound from the group consisting 01' vinyl esters and esters of acrylic and methacrylic acids. 

